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Mourinho's new start almost mirrored his first 16 years ago, when he drew his first La Liga match against Real Mallorca, but substitute Carlos Espí scored a dramatic winning goal in the first minute of stoppage time.
Jude Bellingham opened the scoring after nine minutes, but Alex Calatrava equalized in the 30th minute.
The "Special One" arrives in Madrid with a mission remarkably similar to his previous ones: to end the dominance of Barcelona, the Spanish champions for the past two seasons, at all costs, and help the capital club return to winning ways.
This successful start, despite the less-than-perfect performance, comes ahead of Mourinho's return to the Santiago Bernabéu in his first official match since his 13-year absence, against Real Sociedad on Wednesday in a rescheduled fixture from the first round.
Perhaps the toughest task for Mourinho, known for his fiery personality and leadership skills, will be restoring discipline to a dressing room marked by divisions and rebuilding a competitive team.